Formation of diquaternary salt linkages between two cellulose units by reacting diethylaminoethylated cotton with epichlorohydrin



Feb. 10, 1970 D. M.'SOIGNET' ET AL 3,494,719

- FORMATION OF DIQUATERNARY .SALT LINKAGES BETWEEN TWO CELLULOSE UNITS BY REACTING DIETNYLAMINOETHYIJATED COTTON WITH EPICHLOROHYDRIN Filed June. 16, 1967 I 1 l I 1 9 00 N '5 o m w m (u H INVENTORS DONALD M. SOIGNET RUTH R.BENERITO RA H BERN! ATTORNEYS United States Patent 1C6 3,494,719

Patented Feb. 10, 1970 tion produces a fabric that possesses strong anion ex- 3,494,719 change properties and increases in wet and dry crease FORMATION OF DIQUATERNARY SALT LINK- recovery AGES BETWEEN TWO CELLULOSE UNITS BY RE ACTING DIETHYLAMINOETHYLATED ldpichlorohydrin is capable of reacting with a tertiary COTTON WITH EPICHLOROHYDRIN 5 amme hydrohydroxrde. ThlS reactlon removes the H Donald M. soignet, Metairie, and Ruth Benerito and and the 0H from the tertiary amine hydrohydroxide to Ralph L Berni, New Orleans, La" assignors to the form the free amine. The free amine can react with an- United States of America as represented by the Secreother mole of epichlorohydrin to form the quaternary tary of Agriculture salt which in turn reacts with additional epichlorohydrin Filed June 16, 1967, Ser- No- 646,739 10 to form a polymeric substance containing a terminal epox- D061 13/08 ide group. This polymeric specie can then react with 8-116 1 Clam another tertiary amine to form a diquaternary salt linking two cellulose units together. The following equations show the probable course of this reaction.

ABSIRACT 0F IHE DISCLOSURE 15 C H 2 5 This invention relates to the production of partial cel- 90H lulose ethers with improved resiliency and strong anion exchange properties. More particularly, this invention re- Cell OCHzCHzNIH CICH2C\H}JH2 lates to the reaction of diethylaminoethylated cotton and 2115 O epichlorohydrin to produce a cellulose ether with strong 02m anion exchange properties and improved wet and dry crease resistance. Cell OCH2OH21-CQH5 clOHfilHCgg OH OH A non-exclusive, irrevocable, royalty-free license in the invention herein described throughout the world for all Ce11OCH2CH2N= C1CH2C\HOH2 purposes of the United States Government, with the power 2115 to grant sublicenses for such purposes, is hereby granted CZHS to the Government of the United States of America. 016

A primary object of the present invention is to provide G3 a method for preparing at will some cellulose ethers with Cell 0 CHzCHzNCHzCHCH strong anion exchange properties and improved wet and 5 dry crease recovery.

Prior art processes are known for the preparation of di- CZHE ethylaminoethylated cotton. The method of Hartman 01 (Hartman, lVl., US. Patent 1,777,970, Oct. 7, 1930) pro- Gen OCHZCIgNCHZCHCE MCICHzCHCHZ) duced a fabric that possessed weak anion exchange properties and showed no increase in dry recovery angle. Hoif- O 0 pauir and Guthrie (Hoifpauir, C. L., and Guthrie, J. D., 40 02115 Textile Research Journal 20, 617 (1950)) converted some 9 0 of the tertiary amino groups to quaternary groups by re- 0 H 0C 65 fiuxing with a 10% CH I solution in absolute ethanol. e HZOHZN CHflClCHCHzOCHmHCHZ Benerito (Benerito, R. R., Woodward, B. B., and Guthrie, 2H6

C2115 02115 OH C2H5 (:1 0 02115 or: 01 e a; Cell 0ongciigrfolrgoioHGHgOCHzLQHCHz ZIII-CHZCHQO Cell Cell OCH CHZ-IIICH2(CIOHCH2OCH2)nCHCHrN-CH2CHgO Cell C2135 C2135 C2Hz 2H5 I. D., Analytical Chemistry, 37, 1693 (1965)) found that In the present invention, a cotton fabric is pretreated a larger number of these tertiary amino groups could be with a 10% aqueous solution of B-chloroethyldiethylconverted to quaternary groups using the method of amine hydrochloride. The treated fabric is then dried and Hotfpauir and Guthrie while treating the fabrics under immersed overnight in a 25% aqueous solution of NaOH. anhydrous conditions. It is also known that treating a The fabric is washed in dilute acetic acid to remove fabric with a compound that contains a quaternary amino NaOH, dried and immersed in pure-epichlorohydrin, group and some other active substituent yields a fabric which had been preheated to and maintained at 95 C. with strong anion exchange properties but with only a for 3 hours. The sample is then washed in absolute methslight increase in wet recovery and a decrease in dry reanol, tap water and finally distilled water. The fabric is covery and a decrease in dry recovery. It has also been then ironed dry and equalibrated. shown that epichlorohydrin will add to cellulose if the To determine the ion exchange, an accurately weighed cellulose has been pretreated with NaOH (McKelvey, sample of suflicient weight to give approximately 0.8 meq. J. B., Benerito, R. R., Bernie, R. J., and Burgis, B. G., of replaceable anion was placed in a titration flask con- Journal of Applied Polymer Science, 7, 1371 (1963)). taining exactly 50.00 ml. of a salt solution prepared with Attempts to react epichlorohydrin with fabrics that were conductivity water and kept in a nitrogen atmosphere. not pretreated have been unsuccessful. The sample was allowed to equilibrate overnight in the In contrast to the prior art, this invention relates to titration flask while being stirred with nitrogen gas the formation of quaternary amino groups on cellulose bubbled first into a bubbler containing the given solution without necessitating the use of NaOH as a catalyst or before being bubbled into the titration flask to minimize the maintaining of anhydrous conditions. Also, this invenconcentration changes in the flask. All potentiometric titrations were carried out in specially designed cells of approximately 250 ml. capacity having four ground glass outlets to accommodate the microburet in the center, an inlet-outlet tube for nitrogen, the glass electrode and the saturated calomel electrode. All pH measurements were made with a Beckman Model GS pH meter to a $0.05 pH units. Each titration required from 8-12 hours because of time required in some instances for establishment of equilibrium. FIGURE 1 illustrates the curves (A) of strong and weak (B) ion exchange cotton.

EXAMPLE 1 Approximately g. of an 80 x 80 printcloth, desized, scoured, and bleached was impregnated in a 10% solution of fl-chloroethyldiethylamine hydrochloride for ten minutes. The fabric was dried in an air oven at 60 C. The fabric was then immersed in a 25% aqueous solution of NaOH for a period of 16 hours. The treated fabric, diethylaminoethylated cellulose, was washed in dilute acetic acid, tap water, ironed dry and equilibrated. The nitrogen content of the treated fabric was determined and the above sequence of operations was repeated until a nitrogen content of at least 0.7% was obtained.

EXAMPLE 2 Approximately 9 g. of diethylaminoethylated cotton, prepared as in Example 1 and having a nitrogen content of 0.71% and a wet and dry crease recovery of 213 and 214 (W+F) degrees, was placed in a 100 ml. graduated cylinder containing excess reagent grade epichlorohydrin,

preheated to and maintained at 95 C. for three hours.

After the reaction period, the fabric was washed in absolute methanol followed by washing with tap water and distilled water. The fabric was ironed dry and equilibrated and had a weight gain of 9.2% and a wet and dry crease recovery of 265 and 284 (W+F) degrees. The fabric was titrated as a strong base anion exchange resin.

EXAMPLE 3 crease recovery of 196 and 196 (W+F) degrees was treated as in Example 2. The resulting product had a 4 weight gain of 15.2% and a wet and dry crease recovery of 243 and 288 (W+F) degrees. The fabric was titrated as a strong base anion exchange resin.

EXAMPLE 5 Approximately 10 g. of an x 80 printcloth, designed, scoured and bleached was impregnated in a 10% solution of 13-chloroethyldiethylamine hydrochloride for ten minutes. The fabric was dried in an air oven at 60 C. The fabric was then immersed in a 25 aqueous solution of NaOH for 16 hours. The treated fabric, diethylaminoethylated cellulose, was washed in dilute acetic acid, tap water, and dried over P 0 for 48 hours. The above sequence of operations was repeated until the fabric had a nitrogen content of 1.23% and a wet and dry crease recovery of 196 and 196 (W+F) degrees.

Approximately 8 g. of the above diethylaminoethylated cotton was immersed in excess reagent grade epichloro hydrin, preheated to and maintained at C. for three hours. After the reaction period, the fabric was washed in absolute methanol followed by washings with tap water and distilled water. The fabric was ironed dry and equilibrated and had a wet and dry crease recovery of 233 and 293 (W+F) degrees. The fabric was titrated as a strong base anion exchange resin.

We claim:

1. A process for producing partial cellulose ethers in fabric from which process comprises the following steps:

(a) reacting diethylaminoethylated cotton with a nitro gen content of at least 0.7% with pure epichlorohydrin, preheated to and maintained at 95 C. for a period of about three hours, (b) washing the fabric free of reagents, drying, and

equilibrating the washed fabric.

I References Cited UNITED STATES PATENTS 2,898,310 8/1959 Greer 260-21 3,277,025 10/ 1966 Flodin et a1. 260-2.1

OTHER REFERENCES Holfpauir et al., Textile Research Journal, vol. 20, pp. 617-620 (1950).

Benerito et al., Analytical Chemistry, vol. 37, pp. 1693- 1699 (1965).

GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner US. Cl. X.R. 

